Composition comprising a phosphate binder and its preparation

ABSTRACT

A binder, a composition, a product and a kit, as well as a process for preparing the binder and composition, are directed to a composition useful as an inorganic phosphate binder, which binder is characterized as having calcium silicate sites which are connected the one with the other by alumina-silica phosphate bonds, and a filler.

The present application is a continuation in part application ofInternational Application No. PCT/BE01/00174, with an Internationalfiling date of Oct. 8, 2001, published in English under PCT Article21(2), this continuation in part application further claiming thebenefit of priority of International Application No. PCT/BE03/00121filed on Jul. 7, 2003, which designates the United States and at leastone other country.

FIELD OF THE INVENTION

The present invention relates to a composition comprising an inorganicbinder, most precisely to an inorganic phosphate binder.

THE PRIOR ART

Inorganic phosphate binder have already been proposed in the past.

For example in a previous patent application WO9903797 in the name ofMetal Chemical and Haji Anas, a polymeric matrix is disclosed, saidmatrix comprising a binder formed by mixing an alkali metal silicateaqueous solution with a powder comprising silico-aluminous reactive rawmaterials. A polymerization time of more than one hour is howevernecessary for reaching a sufficient hardening of the matrix.

It has also been proposed in U.S. Pat. No. 6,139,619 to form a binder bymixing a water soluble silicate with a water soluble amorphous inorganicphosphate glass in an aqueous medium. The hardening of the binderrequires the removal of water by a heat treatment.

In U.S. Pat. No. 4,375,551, an acid solution is prepared by mixingAl₂O₃.3H₂O with phosphoric acid, said acid solution being then mixedwith calcium silicate. The so obtained binder has after hardening poormechanical strength.

U.S. Pat. No. 4,504,555 discloses an inorganic resin formed by reactinga first liquid component containing a mono aluminum phosphate or a monomagnesium phosphate, with a second liquid component containing magnesiumoxide and/or wollastonite and a dispersing agent. Inert filler can beadded to the first or second component. The inert filler (particles notparticipating to the reaction) can be SiO₂ particles. The productprepared by this reaction is a resin in which adjacent calcium silicatesites (wollastonite) bound by magnesium/aluminum phosphate bonds, not byalumina silica phosphate bonds.

U.S. Pat. No. 3,179,527 discloses a coating composition formulated byadding silica or lime to an acidic solution of aluminum phosphate.Calcium silicate is then added to the composition. As stated in column 2of said patent, the effect of added silica depends from the particlesize of the silica particles, fine silica particles forming open cracks,while coarser particles do not produce such cracks. The silica particlesare therefore not dissolved, otherwise the particle size of the silicaparticle would have no influence on cracks. The silica is therefore usedin this patent as filler. The use of silica in a prereacted compositionis even not indispensable according to said patent, as it could bereplaced by calcium silicate. Silica is therefore not participating inthe formation of bond between two adjacent calcium silicate particles.The compositions of this patent have a long shelf stability, meaningthat the hardening reaction is a slow process.

The present invention has for subject matter a binder which can besufficiently hardened within a term of less than 10 minutes and whichhas excellent mechanical properties. The inorganic binder of theinvention is characterized by calcium silicate sites connected the oneto the other by alumina-silica phosphate bonds.

DESCRIPTION OF THE INVENTION

The Binder

The inorganic binder of the invention is characterized by calciumsilicate sites which are connected the one with the other byalumina-silica phosphate bonds.

Advantageously, the calcium silicate sites are calcium meta silicatesites having a substantially acicular nature with a length/diameterratio from 2/1 to 50/1, advantageously from 3/1 to 20/1.

Preferably, the calcium meta silicate sites has an average length from10 μm to 10 mm, advantageously from 50 μm to 5 mm.

The calcium silicate sites act preferably as cross-linking sites foralumina-silica phosphate bonds.

According to an embodiment, the alumina-silica phosphate bonds have aweight ratio Al₂O₃/SiO₂ ranging from 0.3:1 and 10:1, advantageously from0.6:1 and 6:1.

According to an advantageously embodiment, the weight ratio calciumsilicate sites/alumina-silica phosphate bonds is comprised between 0.1and 1.1, advantageously between 0.3 and 0.9, preferably between 0.4 and0.7.

The binder of the invention is suitable for preparing product having alight weight (such a weight from 70 to 140 kg/m³) or a heavy weight(such as weight of 2,000 kg/m³ or even more). Products of the inventionhave high mechanical properties, such as compression strength of morethan 40N/mm², bending strength of more than 10 N/mm², etc.

The invention relates also to a composition and a product comprising atleast a binder according to the invention and at least one filler and/orreinforced material.

Compositions of the Invention

The compositions of the invention are composition before hardening,after hardening, possibly after an after treatment, such as a dryingstep, a heating step, etc.

Compositions of the inventions are compositions comprising at least abinder of the invention, and one or more fillers, inert fillers with thebinder.

The composition of the invention comprising at least:

-   an inorganic binder having calcium silicate sites which are    connected the one with the other by alumina-silica phosphate bonds,    the calcium silicate sites acting as cross-linking sites for the    alumina-silica phosphate bonds with a weight ratio Al₂O₃/SiO₂    ranging from 0.3:1 to 10:1, advantageously from 0.6:1 to 6:1, and-   a filler.

Examples of fillers or reinforced materials which can be mixed with thebinder before its preparation, during its preparation, before itshardening or during its hardening are:

-   waste materials, such as finely divided waste material, for example    fuel ashes, fly ashes, buildings waste materials, etc.-   flake-like materials such as mica, etc.,-   silica sand, silica flour,-   coloring agents or materials, such as inorganic coloring agents,    pigments, etc.-   cellulose and/or protein base fibers, such as natural fibers, flax,    chip, straw, hemp, wool fibers, etc.-   synthetic fibers, such as organic synthetic fibers, inorganic    synthetic fibers, such as polyesters, polypropylene, glass and    ceramic fibers, etc.-   natural and synthetic organic base waste materials, such as saw    dust, rice husk, straw and recycled organic waste,-   natural fibers of mineral origin,-   natural material, possibly treated (for example heat treated), such    as perlite, vermiculite, etc.-   etc.-   mixtures of one or more of the above fillers.

Specific examples of possible fillers are:

-   rice husk,-   waste recycle cardboard-   shredded paper-   rice husk/shredded paper composite-   rice husk+waste recycle cardboard-   pine needle-   laminated elements, such as honeycomb board, normal cardboard, etc.-   pigments

Additives can be added to the binder before its preparation, during itspreparation, before its hardening or during its hardening, suchadditives are for example:

-   foaming agents, such as water peroxide, organic peroxide, etc.-   viscosity regulating agent, such as superplasticizer-   material for improving the impermeability or the water repulsion    such as lignosulfonates and silica fume-   etc.

According to an embodiment, substantially all calcium silicate sites ofthe inorganic binder are bound the one to the other by alumina-silicaphosphate bonds.

According to a specific embodiment, the weight ratio calcium silicatesite/SiO₂ present in the alumina-silica phosphate bonds of the inorganicbinder is greater than 1, advantageously greater than 1.5, such as 2, 3,4, 5 or even more.

The calcium silicate particles are advantageously calcium meta silicateparticles having a substantially acicular nature with a length/diameterratio from 2/1 to 50/1, advantageously from 3/1 to 20/1.

The calcium meta silicate particles have preferably an average lengthfrom 10 μm to 10 mm, advantageously from 50 μm to 5 mm, such as 100 μm,300 μm, 500 μm, etc.

According to a preferred embodiment, the calcium silicate particles actas cross-linking sites for alumina-silica phosphate bonds. It seems alsothat the presence of insoluble calcium silicate particles catalyzes theformation of alumina-silica phosphate bonds.

For example, the weight ratio calcium silicate particles/alumina-silicaphosphate solution is comprised between 0.1 and 1.1, preferably from 0.3and 0.9, most preferably between 0.4 and 0.7.

Preferably, the composition comprises at least a silicon containingfiller, most preferably silicon containing fibers with a length of lessthan 1000 μm. The weight content of silicon containing fibers with alength of less than 1000 μm in the composition after its hardening andafter removal of the possible free water is advantageously at least0.5%. The silica containing fillers, especially fibers, areadvantageously treated with a water repellent agent, such as a waterrepellent coating of less than 10 μm. This coating is for example afluoro silane coating.

It has now further been observed that by using specific filler,especially a combination of specific fillers, it was possible toincrease mechanical properties of the mixture binder/filler(s) and/orthe final appearance of the composition after its hardening and/or thefire resistance of the composition. For example, it was observed thatswelling of the product could be reduced or prevented after a waterabsorption.

The invention relates thus also to a composition comprising at least:

-   an inorganic binder having calcium silicate sites which are    connected the one with the other by alumina-silica phosphate bonds,    the calcium silicate sites acting as cross-linking sites for    alumina-silica phosphate bonds with a weight ratio Al₂O₃/SiO₂    ranging advantageously from 0.3:1 and 10:1, preferably from 0.6:1    and 6:1, and-   silicon containing fibers with a length of less than 1000 μm, the    weight content of silicon containing fibers with a length of less    than 1000 μm in the composition after its hardening and after    removal of the possible free water being of at least 0.5% (i.e. a    dry weight content).

It has been observed that the presence of at least 0.5% by weight,preferably at least 1% by weight of silicon containing fibers,advantageously silicon containing fibers non reactive with the binder orsubstantially non reactive with the binder, it was possible to preventthe formation of any cracks at the surface of the hardened composition,as well as advantageously in the body of the hardened composition, evenif the hardened composition has a high thickness, such as a thickness ofmore than 2 mm, advantageously of more than 5 mm, such as a thicknesscomprised between 10 mm and 50 mm.

Advantageously, the composition comprises silicon containing fibers withan average (in weight) length of less than 500 μm, the weight content ofsilicon containing fibers with an average length of less than 500 μm inthe composition after its hardening and after removal of the possiblefree water (free water is water present in the composition, such as inthe hardened composition, but which can be removed in a drying step at atemperature of 100° C.) being of at least 0.5% (i.e. a dry weightcontent).

According to a preferred embodiment, the composition comprises siliconcontaining fibers with an average (in weight) length of more than 10 μm,advantageously of more than 20 μm, preferably comprised between 25 μmand 300 μm, most preferably between 50 μm and 250 μm.

According to an advantageous embodiment, the silicon containing fiberswith a length of less than 1000 μm, advantageously with an average (inweight) length of less than 500 μm, are substantially not reactive withthe binder, preferably not reactive with the binder, i.e. acting as apure filler. Substantially not reactive silicon containing fibers arefibers characterized in that less than 10% by weight, advantageouslyless than 5% by weight, preferably less than 1% by weight, mostpreferably less than 0.5% by weight, of the silicon containing fibers ischemically reacted with the binder, for making for example one or morechemical bonds between fibers and the binder.

According to embodiments, after hardening and removal of free water, thecomposition comprises from 1% up to 75% by weight, advantageously from2% up to 25% by weight, silicon containing fibers with a length of lessthan 1000 μm, advantageously with an average (in weight) length of lessthan 500 μm.

Silica containing fibers are for example natural fibers, possiblytreated, synthetic fibers, mineral fibers, and mixtures thereof. Naturalfibers are preferred, such as wood fiber, straw fiber, rice husk or branfibers, mixtures thereof. The natural fibers are advantageously heattreated, for example at temperature higher than 400° C., such as at atemperature higher than 700° C. or 800° C., advantageously in anatmosphere rich in Nitrogen or in a nitrogen atmosphere. Said heattreatment is preferably carried after a drying step. Rice bran or ricehusk are preferred silica containing fibers used in the composition ofthe invention, said fibers being advantageously defatted and dried. Whensaid fibers are burned and carbonized in a nitrogen gas rice branceramic fiber are produced. Possibly some phenolic resin is added to therice bran or rice husk before the carbonizing and burning step. Possiblythe phenolic resin can be mixed with rice bran so as to prepare or formrice bran containing fibers or filaments, the latter fibers or filamentafter drying being carbonized and burnt (for example at a temperature of300 to 1100° C. during a time sufficient for the formation of ceramics).The silica containing fibers are advantageously ceramic silicacontaining fibers. Such fibers, especially rice bran ceramic fibers,have a high strength, a high hardness, a low density, a low friction(hereby the fibers can easily flow the one with respect to the other,whereby facilitating the mixing step).

Silica containing fibers are advantageously treated with a waterrepellent agent, such as a water repellent coating of less than 10 μm.This coating is for example a fluoro silane coating.

According to a preferred embodiment, the composition further comprisessilica flour with a particle size of less than 500 μm, advantageouslycomprised between 2 and 400 μm, the weight content of silica flour inthe composition after its hardening and after removal of the possiblefree water being of at least 0.5%. Said silica flour content isadvantageously comprised between 1 and 10% by weight of the compositionafter its hardening and removal of free water (water which can beremoved with a heating step at a temperature of 100° C.) (i.e. a dryweight content).

Preferably, the composition comprises silica flour with an average (inweight) particle size comprised between 2 and 100 μm, advantageouslybetween 5 and 60 μm, preferably between 10 and 50 μm, the weight contentof silica flour in the composition after its hardening and after removalof the possible free water being comprised between 1 and 10%,advantageously between 2 and 8%.

According to a more specific embodiment, the composition with or without(advantageously with) silica flour further comprises crystallizedalumina silicate particles which are substantially not reactive with thebinder and which have an average (in weight) particle size comprisedbetween 5 and 100 μm, the weight content of crystallized aluminasilicate in the composition after its hardening and after removal of thepossible free water being comprised between 1 and 10%, advantageouslybetween 2 and 8%.

According to an advantageous embodiment, the weight ratio calciumsilicate site/SiO₂ present in the alumina-silica phosphate bonds isgreater than 1, preferably greater than 1.5.

Advantageously, the calcium silicate sites are calcium meta silicatesites having a substantially acicular nature with a length/diameterratio from 2/1 to 50/1, advantageously from 3/1 to 20/1.

Preferably, the calcium meta silicate sites has an average length(average in weight) from 10 μm to 10 mm, advantageously from 50 μm to 5mm, such as 100 μm, 300 μm, 500 μm.

The calcium silicate sites act preferably as cross-linking sites foralumina-silica phosphate bonds.

According to an embodiment, the alumina-silica phosphate bonds have aratio Al₂O₃/SiO₂ ranging from 0.3:1 and 10:1, advantageously from 0.6:1and 6:1.

According to an advantageously embodiment, the weight ratio calciumsilicate sites/alumina-silica phosphate bonds is comprised between 0.1and 1.1, advantageously between 0.3 and 0.9, preferably between 0.4 and0.7.

The composition of the invention can also comprise one or more furtherfiller(s) and/or reinforced materials.

The composition, as well as the binder of the invention can be used forattaching two elements together, i.e. as glue, heat resistant glue orsealant.

Product

The invention relates also to a product comprising at least a hardenedlayer comprising an inorganic binder of the invention as disclosedhereinabove in the paragraph relating to the binder, but preferablyhaving the composition of the invention as disclosed hereinabove.

The binder/composition of the invention is suitable for preparingproduct having a light weight (such a weight from 70 to 140 kg/m³) or aheavy weight (such as weight of 2,000 kg/m³ or even more).

Products of the invention have high mechanical properties, such as oneor more of the following properties (preferably several of saidproperties): compression strength of more than 40N/mm², bending strengthof more than 10 N/mm², very low heat of combustion (less than 500 KJ/kg,advantageously less than 100 KJ/kg, method used: ASTM D 2015 and BS ENISO 1716), a high modulus of rupture (such as more than 10 MPa, forexample between 12 and 20 MPa, method of analysis: NBN EN 196-1), a highcompressive strength (more than 50 MPa, such as from 70 to 100 MPa,method of analysis: NBN EN 196-1), a high Young's modulus (more than 500MPa, such as between 8000 and 15000 MPa, method of analysis: NBN EN196-1), absence of swelling even for water absorption from 10% up to 30%depending of the porosity, etc.

Products of the invention can be used as insulating materials (aspanels, sheets, granules, etc), fire protection material, heatprotection material, chemical protection material, buildings material(such as bricks, concrete, etc.), for making molds, shaping, casting andmoldings products, tiles, roofing sheet, coating layers, inner layer,laminated products, metallic profile, aluminum profile, steel profile,metal band or plate, flexible membrane, polyethylene web. Polymer layer(polyurethane, latex, etc.), etc. Specific examples are: roofing sheet,insulation panels, coating surface material.

Wear resistant tile, high strength building elements, fire and heatresistant elements, adhesive material, sealants, slates, laminatedelements, joint compounds, refractory, mineral fibers, etc.

The invention relates also more precisely to a product made at leastpartly or associated at least partly to a hardened composition of theinvention, as disclosed here above. For example the product can be asupport provided with a coating layer with a thickness for example of 1to 10 mm, or even more.

The product can also have the form of a laminated product, an innerlayer being made from a composition of the invention, said inner layerhaving for example a thickness of 5 mm up to 100 mm, or even more.

According to an embodiment, the hardened layer covers at least partly aface of a support element. One or more faces of the support can beprovided with a hardened layer. The thickness of the layer isadvantageously lower than 10 mm, such as lower than 5 mm, such as 4 mm,3 mm, 2 mm, 1 mm, 500 μm, 250 μm, 100 μm, depending on the propertieswhich are required.

According to an advantageous embodiment, the hardened layer covers atleast partly a face of a support comprising a core which can besubjected to a water swelling. It has been observed that by coatingalready one face of a plate (which can be subjected to a water swelling)with a composition of the invention, it was possible to obtain afterhardening of the composition, a product which has a reduced swellingeven after being dipped in water for 72 hours at 20° C. Tests made oncommercial wood fiber composite material with a swelling of 37% afterbeing dipped in water for 72 hours at 20° C., have shown that byproviding one or more faces of the material with a thin hardened layerof the composition of the invention, it was possible to reduce theswelling to less than 10%, advantageously less than 6%, preferably lessthan 2%.

According to a specific embodiment, at least partly a face not coveredby a hardened layer of the invention is provided with a water repellentcoating, advantageously silicon containing water repellent coating, suchas a fluoro silicon coating (fluoro silane, etc. such as fluorosilanemarketed by 3M as water repellent agent, such as the productScotchgard®).

The thickness of the water repellent coating is advantageously less than500 μm, such as less than 250 μm, preferably less than 150 μm, mostpreferably less than 100 μm, for example less than 50 μm, or evenlesser, such as less than 20 μm or even less than 10 μm.

According to a more specific embodiment, substantially all the faces notcovered with the hardened layer are provided with a water repellentcoating.

According to an embodiment, the support has two substantially parallelfaces (top and bottom faces or major faces, front and rear faces)connected the one to the other by lateral faces, whereby said lateralfaces (bottom/top or front/rear faces) have a higher water permeabilitythan the two substantially parallel faces. In said embodiment, thelateral faces of the support are provided with a water repellentcoating. The water repellent coating on said lateral faces covers alsoat least a portion of the front/rear faces along their edges or at leasta portion of the hardened layer adjacent to the edges of said front andrear faces. The water repellent coating can be carried out before and/orafter providing the support with the hardened layer of the invention.

The Kit

The invention relates also to a kit for the preparation of inorganicbinder composition according to the invention, said kit comprising:

-   a container of bag containing a water insoluble calcium silicate,    and-   one or more containers or bags containing compounds for preparing an    acid alumina-silica phosphate solution, the pH of said solution    measured at 20° C. being less than 1.5, advantageously less than 1,    preferably less than 0.5.

The acid pH is advantageously obtained by using phosphoric acid or anacid mixture containing at least phosphoric acid. Preferably,substantially only phosphoric acid is used as mineral acid, mostpreferably as acid for lowering the pH of the solution to less than 2.The acid can be in a distinct container or can be used for thepreparation of an acid solution containing solubilized alumina-silicaphosphate, i.e. a ready to mix solution.

According to a preferred embodiment of the kit, the kit comprises:

-   a container of bag containing a water insoluble calcium silicate,    silicon containing fibers with a length of less than 1000 μm, and    possibly, but advantageously also silica flour with an average    particle size of less than 500 μm, and-   one or more containers or bags containing compounds for preparing an    acid alumina-silica phosphate solution or containing an    alumina-silica phosphate solution, the pH of said solution measured    at 20° C. being less than 1.5, advantageously less than 1,    preferably less than 0.5, in which the silica is solubilized.

It has been observed that the premix of water insoluble calcium silicatewith silicon containing fibers with a length of less than 1000 μm was ina form enabling an easily and quick mixing with an acid alumina-silicaphosphate solution.

The water insoluble calcium silicate, the silicon containing fibers, thesilica flour used in the kit has advantageously one or morecharacteristics as disclosed here above in the binder and compositionsof the invention.

The alumina-silica phosphate solution has advantageously a weight ratioAl₂O₃/SiO₂ ranging from 0.3:1 and 10:1, preferably from 0.6:1 and 6:1.

The kit advantageously further comprises a container with a compositioncontaining a water repellent agent, advantageously in the form of asolution, preferably a ready to use solution. Such a composition is forexample a water based solution or a solvent based solution containing awater repellent silane, preferably a fluoro silane.

The Process for the Preparation of a Binder/Composition of the Invention

A further subject matter of the invention is a process for thepreparation of a binder/composition according to the invention, in whichwater insoluble calcium silicate particles are mixed with an acidalumina-silica solution at a temperature lower than 50° C., said acidalumina-silica solution having a pH less than 2, advantageously lessthan 1.5, for example comprised between 0.1 and 1.5, preferablycomprised between 0.5 and 1.5.

The acid pH is advantageously obtained by using phosphoric acid or anacid mixture containing at least phosphoric acid. Preferably,substantially only phosphoric acid is used as mineral acid, mostpreferably as acid for lowering the pH of the solution to less than 2.

In the process of the invention, the alumina-silica phosphate solutionhas advantageously a ratio Al₂O₃/SiO₂ ranging from 0.3:1 and 10:1,preferably from 0.6:1 and 6:1.

In the process of the invention, a filler and/or a reinforced materialis advantageously mixed with the calcium silicate particles before beingmixed with the acid alumina-silica phosphate solution and/or a fillerand/or a reinforced material is mixed to the mixture calciumsilicate/alumina-silica phosphate solution, before or during itshardening.

Preferably, the hardening of the binder is carried out at a temperaturecomprised between 0° C. and 50° C., possibly under pressure.

The binder of the invention is prepared by using an acid alumina-silicaphosphate solution, said solution is advantageously prepared by reactingaluminum oxide powder (size advantageously lower than 50 μm, preferablylower than 30 μm, for example from 5 to 25 μm) with a purity of morethan 95%, preferably more than 99%, silica powder (size advantageouslylower than 50 μm, preferably lower than 30 μm, for example from 10 to 25μm) with a purity of more than 95%, preferably of more than 99%, andphosphoric acid as an aqueous phosphoric acid or in presence of anaqueous medium. The phosphoric acid has preferably a purity of more than95%, most preferably of more than 99%. Phosphoric acid is available invarious concentration. Preferably, the phosphoric acid will be aphosphoric aqueous solution with a phosphoric acid concentration of morethan 75%, preferably of more than 85%. Preferably, the silica powder isfirst mixed with the phosphoric acid and then the alumina particles areadded.

The acid alumina-silica phosphate solution contains possibly some otheracids, such as organic acid, strong mineral acid, etc, however, in thiscase, the content of such acid will preferably be less than 10% of thephosphoric acid content of the solution.

Instead of using aluminum oxide, it is possible to use aluminumphosphate, aluminum hydroxide, etc. However, aluminum oxide ispreferred.

Instead of using silica, preferably precipitated silica particles, it ispossible to use waste material issuing from glass bottles.

Possibly the aqueous phosphoric acid solution contains other solvents,such as alcohol, etc.

When a foamed product is desired, more water or solvent will be used fordecreasing as much as possible the viscosity.

The acid alumina silica phosphate solution has advantageously a pH lowerthan 2, preferably lower than 1.

It has been observed that when using silica particles for thepreparation of the acid alumina phosphate solution with a pH lower than2, most preferably lower than 1, the dissolution of alumina particleswas improved. The presence of solubilized SiO₂ in the acid solution wasalso improving the formation of the bonds when adding the waterinsoluble calcium silicate particles. Even, if some calcium silicateparticles are solubilized due to the low pH, some calcium silicateparticles remains insoluble, due for example to the increase of pH to avalue comprised between 3 and 6.

According to a specific embodiment, the process for the preparation of acomposition according to the invention is a process, in which a bindingmixture is prepared by mixing water insoluble calcium silicate particleswith an acid alumina-silica phosphate solution at a temperature lowerthan 50° C., said acid alumina-silica phosphate solution comprisingsolubilized SiO₂ and having a pH less than 2, advantageously less than1.5, preferably comprised between 0.5 and 1.5, said alumina-silicaphosphate solution having a weight ratio Al₂O₃/SiO₂ rangingadvantageously from 0.3:1 and 10:1, preferably from 0.6:1 and 6:1, inwhich silicon containing fibers with a length of less than 1000 μm aremixed with water insoluble calcium silicate particles, prior to orduring the mixing of water insoluble silicate particles with an acidalumina-silica phosphate solution and/or in which silicon containingfibers with a length of less than 1000 μm are mixed with the bindingmixture before its complete hardening.

Preferably, the binding mixture is first prepared and then the siliconcontaining fibers are added. Said addition is carried out when thebinding mixture is still sufficiently liquid or pourable by gravity.Possibly before and/or during the addition of the fibers, water can beadded for controlling the viscosity. Possibly the silicon containingfibers are prewetted before being added to the binding mixture.

According to an advantageous embodiment, silica flour is added to thewater insoluble calcium silicate particles, prior to or during themixing of water insoluble silicate particles with an acid alumina-silicaphosphate solution and/or to the binding mixture before its completehardening, said addition being carried out prior, during or after theaddition of silicon containing fibers.

Preferably, the silicon containing fibers and the silica flour arepremixed before being added to the acid alumina-silica phosphatesolution or to the binding mixture.

According to a possible embodiment, the insoluble calcium silicateparticles, the silicon containing fibers and the silica flour arepremixed before being added to and mixed with the acid alumina-silicaphosphate solution.

Advantageously, the weight ratio water insoluble calcium silicateparticles/solubilized SiO₂ present in the alumina-silica phosphatesolution is greater than 1, preferably greater than 1.5.

Preferably, the hardening of the binder/composition is carried out at atemperature comprised between 0° C. and 50° C., such as advantageouslybetween 10 and 30° C.

The binder/composition is preferably hardened under pressure, such asunder a pressure comprised between 2 10⁵ Pa and 100 10⁵ Pa, for example5 10⁵ Pa, 10⁶ Pa, 2 10⁶ Pa, etc.

The amount of calcium silicate added to the acid silica aluminaphosphate solution is advantageously such that the weight ratio calciumsilicate/SiO₂ present in the acid solution is comprised between 1 and 5,advantageously comprised between 1.5 and 3.5.

Preferably, the amount of calcium silicate added to the acid silicaalumina phosphate solution is such that the weight ratio calciumsilicate/SiO₂ present in the acid solution is greater than 2.

According to a preferred embodiment, the silica used for the preparationof the acid silica alumina phosphate solution is precipitated silica.

The acid alumina-silica solution before its mixing with insolublecalcium silicate particles has advantageously a pH of less than 2,preferably less than 1.5, for example comprised between 0.1 and 1.5,preferably comprised between 0.5 and 1.5. The acid pH is advantageouslyobtained by using phosphoric acid or an acid mixture containing at leastphosphoric acid. Preferably, substantially only phosphoric acid is usedas mineral acid, most preferably as acid for lowering the pH of thesolution to less than 2.

The calcium silicate particles are advantageously calcium meta silicateparticles having a substantially acicular nature with a length/diameterratio from 2/1 to 50/1, advantageously from 3/1 to 20/1.

The calcium meta silicate particles have preferably an average lengthfrom 10 μm to 10 mm, advantageously from 50 μm to 5 mm.

According to a preferred embodiment, the calcium silicate particles actas cross-linking sites for alumina-silica phosphate bonds. It seems alsothat the presence of insoluble calcium silicate particles catalyzes theformation of alumina-silica phosphate bonds.

In the process of the invention, the alumina-silica phosphate solutionhas advantageously a weight ratio Al₂O₃/SiO₂ ranging from 0.3:1 and10:1, preferably from 0.6:1 and 6:1.

For example, the weight ratio calcium silicate particles/alumina-silicaphosphate solution is comprised between 0.1 and 1.1, preferably from 0.3and 0.9, most preferably between 0.4 and 0.7.

In the process of the invention, various filler and/or a reinforcedmaterial can be mixed with the calcium silicate particles before beingmixed with the acid alumina-silica phosphate solution, and/or a fillerand/or a reinforced material is mixed to the mixture calciumsilicate/alumina-silica phosphate solution, before its or during itshardening.

Examples of fillers or reinforced materials which can be mixed with thebinder before its preparation, during its preparation, before itshardening or during its hardening are:

-   waste materials, such as finely divided waste material, for example    fuel ashes, fly ashes, buildings waste materials, etc.-   flake-like materials such as mica, etc.,-   silica sand, silica flour,-   coloring agents or materials, such as inorganic coloring agents,    pigments, etc.-   cellulose and/or protein base fibers, such as natural fibers, flax,    chip, straw, hemp, wool fibers, etc.-   synthetic fibers, such as organic synthetic fibers, inorganic    synthetic fibers, such as polyesters, polypropylene, glass and    ceramic fibers, etc.-   natural and synthetic organic base waste materials, such as saw    dust, rice husk, straw and recycled organic waste,-   natural fibers of mineral origin,-   natural material, possibly treated (for example heat treated), such    as perlite, vermiculite, etc.-   etc.

Additives can be added to the binder/composition before its preparation,during its preparation, before its hardening or during its hardening,such additives are for example:

-   foaming agents, such as water peroxide, organic peroxide, etc.-   viscosity regulating agent, such as superplasticizer-   material for improving the impermeability or the water repulsion    such as lignosulfonates and silica fume-   etc.

Possibly, additives or fillers can be added during or after thehardening, for example for making a top coat.

The binder/composition of the invention is prepared by using an acidalumina-silica phosphate solution, said solution is advantageouslyprepared by reacting aluminum oxide powder (size advantageously lowerthan 50 μm, preferably lower than 30 μm, for example from 5 to 25 μm)with a purity of more than 95%, preferably more than 99%, silica powder(size advantageously lower than 50 μm, preferably lower than 30 μm, forexample from 10 to 25 μm) with a purity of more than 95%, preferably ofmore than 99%, and phosphoric acid as an aqueous phosphoric acid or inpresence of an aqueous medium. The phosphoric acid has preferably apurity of more than 95%, most preferably of more than 99%.

Phosphoric acid is available in various concentration. Preferably, thephosphoric acid will be a phosphoric aqueous solution with a phosphoricacid concentration of more than 75%, preferably of more than 85%.Preferably, the silica powder is first mixed with the phosphoric acidand then the alumina particles are added.

The acid alumina-silica phosphate solution contains possibly some otheracids, such as organic acid, strong mineral acid, etc, however, in thiscase, the content of such acid will preferably be less than 10% of thephosphoric acid content of the solution.

Instead of using aluminum oxide, it is possible to use aluminumphosphate, aluminum hydroxide, etc. However, aluminum oxide ispreferred.

Instead of using silica, preferably precipitated silica particles, it ispossible to use waste material issuing from glass bottles.

Possibly the aqueous phosphoric acid solution contains other solvents,such as alcohol, etc.

When a foamed product is desired, more water or solvent will be used fordecreasing as much as possible the viscosity. It is also possible toobtain a foaming product by applying the acid composition on a basecontaining support or on an alkaline support.

The acid alumina silica phosphate solution has advantageously a pH lowerthan 2, preferably lower than 1.

It has been observed that when using silica particles for thepreparation of the acid alumina phosphate solution with a pH lower than2, most preferably lower than 1, the dissolution of alumina particleswas improved. The presence of solubilized SiO₂ in the acid solution wasalso improving the formation of the bonds when adding the waterinsoluble calcium silicate particles. Even, if some calcium silicateparticles are solubilized due to the low pH, some calcium silicateparticles remains insoluble, due for example to the increase of pH to avalue comprised between 3 and 6.

EXAMPLES

Details and characteristics of the invention will appear from thedescription of the following examples.

In said examples, the following products have been used:

-   WATER: water with a low calcium/magnesium content (less than 100    ppm)-   SiO₂: precipitated SiO₂ particles with an average size of 10-15    μm—purity of 99%-   Al₂O₃: powder with an average particle size of 10-15 μm—purity of    99%-   Phosphoric acid: aqueous solution containing 90% phosphoric acid-   Calcium silicate: calcium meta silicate powder, water insoluble,    acicular nature, length of 1 mm, diameter 100 μm.-   Rice Husk fibers (RHF1): dried natural fibers (water content less    than 2%) with an average (in weight) length of about 100 μm.-   Rice Husk fibers (RHF2): dried natural fibers (water content less    than 2%) with an average (in weight) length of about 200 μm.-   Rice bran ceramic fiber (RBCF1): defatted bran mixed with phenolic    resin, shaped in filament, dried and carbonized and burnt under    nitrogen atmosphere at 800° C., the fibers having a length of about    100 μm.-   Rice bran ceramic particles (RBC): defatted bran mixed with phenolic    resin, powdered, dried and carbonized and burnt under nitrogen    atmosphere at 800° C., the powder having an average particle size    (average in weight) of about 50 μm.-   Crystallized alumina silicate (CAS): not reactive with the phosphate    solution, the particles having an average particle size of 50 μm    (average in weight).-   Silica Flour (SF): average (in weight) particle size of about 30 μm-   Silica fume (Sf): average (in weight) particle size 50 μm.-   Glass fiber (GF): glass fibers with a length of 50 μm to 250 μm,    which have been treated with a water repellent agent (fluoro silane)

Examples of Binders

The binders have been prepared by adding SiO₂ particles to phosphoricacid. After dissolution of the SiO₂ particles, Al₂O₃ particles wereadded. An acid alumina silica phosphate aqueous solution was soprepared. The pH of said acid solution was then measured at 20° C.Possibly some water was added.

To said acid solution, calcium silicate particles was added. 5 to 10minutes after the addition of calcium silicate particles, the binder canbe hardened. Said hardening can be made at room temperature. In order tocontrol the viscosity of the mixture, water can be added.

The following table gives the composition of the binders prepared.

Binder 1 2 3 4 5 6 7 8 9 10 SiO₂ (g) 35 16 21 13.6 46.2 60 182 130.897.2 233 Al₂O₃ 24 23 13 50.8 30.8 60 136.5 21.8 58.1 46.6 (g) Phosphoric141 141 167 123 135.6 180 182 87.4 184.7 350.4 acid (g) Molar 0.43 0.20.2 0.19 0.59 0.58 1.73 2.62 0.92 1.15 Ratio SiO₂/P₂O₅ Of the solutionCalcium 120 100 150 60 100 150 200 140 240 310 silicate (g) Water (ml)80 40 25 60 118 21 71 65 pH of the 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.50.5 acid solution pH of the 1 0.5 1 0.5 0.5 1.5 1 1 1.5 1.5 solutionafter addition of the calcium silicate Appearance LS LS S-D S-D P LS LSS-D P P of the mixture after the addition of the calcium silicate (LS,S-D, P)* *LS = Liquid suspension/S-D = Semi-dry/P = Pasty

In the process of the invention, the amount of calcium silicate added tothe acid silica alumina phosphate solution is such that the weight ratiocalcium silicate/SiO₂ present in the acid solution is advantageouslygreater than 1, preferably greater than 1.5, most preferably greaterthan 2, for example comprised between 1 and 5, advantageously comprisedbetween 1.5 and 3.5.

The binders 3 to 5 and 8 to 10, after their preparation, are mixed withwater so as to have a more liquid appearance, whereby the addition offibers and other particles is more adequate.

Examples of Compositions of the Invention

The binder n°2 which is liquid after its preparation was mixed withvarious additives and/or filler.

The following tables gives the different additives and fillers used,expressed in part by weight, the binder being expressed as dry matter(without water).

TABLE 1 Product n° 1 2 3 4 5 6 7 8 Binder (dry 1 1 1 1 1 1 1 1 matter,part by weight) RHF1 0.1 0.1 0.5 RHF2 0.1 RBCF1 0.2 0.4 0.4 0.4 RBC 0.3CAS 0.2 SF 0.02 0.02 0.05 0.05 0.1 0.1 0.1 0.1 Sf 0.1 0.2 0.2 GF 0.5 1

TABLE 2 Product n° 9 10 11 12 13 14 Binder (part 1 1 1 1 1 1 by volume)Additive H₂O₂ Silica Aluminum Super Ligno- Quartz (Part by 0.13 Fumepowder Plasticizer Sulfonate 0.54 volume) 0.42 0.12 0.15 0.13 FillerVermiculite Straw Fly ash Chip Flax Silica (part by 0.33 3 parts 0.521.22 Fiber Flour volume) 0.75 0.25 Appearance Foam, Low Foam Low LowHeavy of the product low density density Low density density densitydensity

For the preparation of said compositions, water can be added forcontrolling the viscosity of the composition, said viscosity beingpreferably maintained as low as possible during the mixing step.

To the compositions of Table 1, one or more further additives or fillerscan be added.

The following table gives possible additives and fillers which can beadded to the compositions of the table 1. Said addition is carried outwhen the composition is sufficient liquid. Possibly some water is addedbefore the addition and/or during the addition of said additives andfillers.

Examples of possible additive and filler added to one volume of acomposition with a solid content of 25% and 50% by weight Additive H₂O₂Silica Aluminum Super Ligno- Quartz (Part by 0.13 Fume powderPlasticizer Sulfonate 0.54 volume) 0.42 0.12 0.15 0.13 FillerVermiculite Straw Fly ash Chip Flax Silica (part by 0.33 3 parts 0.521.22 Fiber Flower volume) 0.75 0.25 Appearance Foam, Low Foam Low LowHeavy of the product low density density Low density density densitydensity

The composition comprising one or more inert fillers are preferablyprepared by premixing at least partly the inert fillers with the calciumsilicate, before using said calcium silicate for the preparation of thebinder. The premix was thus mixed with the acid silica alumina phosphatesolution.

Examples of Coating Operation

A wood board with a thickness of 20 mm has been cut in samples with asize of 200 mm×200 mm. One sample was used as control sample. Saidcontrol sample was dipped in water at 20° C. for 72 hours. The waterabsorption of the control sample was 46% (i.e. the weight of the woodboard was increased by 46% due to the dipping in water, with respect tothe weight of the dry board before its dipping—dry meaning a watercontent of less than 10% by weight in the board), while the swelling ofthe product was 37% (i.e. the volume of the sample was increased by 37%due to the dipping with respect to the volume of the dry board—drymeaning a water content of less than 10% by weight),

The samples have been submitted respectively to the following treatment.

Sample 1

Composition 7 of Table 1 has been used just after its preparation forcoating the upper face of sample. The coating after drying had athickness of 2 mm.

After its complete curing, the sample was dipped in water (20° C.) for72 hours. The water absorption was about 25% with a swelling of about8%.

Sample 2

Sample 2 was prepared as disclosed for sample 1, except that aftercoating the front face, the rear face was also coated with a mm thickcoating (composition 7 of Table 1).

After its complete curing of the two coating layer, the sample wasdipped in water (20° C.) for 72 hours. The water absorption was about20% with a swelling of about 6%.

Sample 3

Sample 3 was prepared as disclosed for example 2, except that thereafterthe four lateral faces of the sample were also provided with a coatinglayer (composition 7), said layer having a thickness of about 1-2 mm.

After complete curing or hardening of the coating layer, the sample wasdipped in water (20° C.) for 72 hours. The water absorption was about14% with a swelling of about 2%.

Sample 4

Sample 4 was prepared as disclosed in example 2, except that the lateralfaces were treated with a water repellent agent (scotchgard™ 3M).

After the complete curing of the two coating layer and of the waterrepellent agent, the sample was dipped in water (20° C.) for 72 hours.The water absorption was about 14% with a swelling of about 0%.

Sample 5

Sample 4 was prepared as disclosed in example 1, except that the lateralfaces were treated with a water repellent agent (scotchgard™ 3M).

After the complete curing of the two coating layer and of the waterrepellent agent, the sample was dipped in water (20° C.) for 72 hours.The water absorption was about 15% with a swelling of about 0-2%.

Sample 6

Sample 6 was prepared as disclosed in example 2, except that before thecoating of the rear and front faces with the composition 7 of Table 1,the lateral faces as well as the edges of the front and rear faces weretreated with a water repellent agent.

After the complete curing of the two coating layer and of the waterrepellent agent, the sample was dipped in water (20° C.) for 72 hours.The water absorption was about 14% with a swelling of about 0-2%.

Sample 7

Sample 7 was prepared as disclosed for sample 3, except that thereafterthe hardened layer was further coated with a water repellent agent(scotchgard).

After the complete curing of the two coating layer and of the waterrepellent agent, the sample was dipped in water (20° C.) for 72 hours.The water absorption was about 15% with a swelling of about 0-2%.

Sample 8

Sample 8 was prepared as disclosed for sample 3, except that beforeapplying the hardened layer of composition 7, all the faces of thesample were coated with a water repellent agent (scotchgard).

After the complete curing of the two coating layer and of the waterrepellent agent, the sample was dipped in water (20° C.) for 72 hours.The water absorption was about 15% with a swelling of about 0-2%.

The water absorption and swelling tests was repeated with orientedstrand board. The conclusions of the samples 1 to 8 were maintained.

The composition 6 was applied on a face of a polyethylene web of 200g/m². After hardening of the composition, a flexible film layer wasobtained.

The composition 8 was poured so as to produce samples for being testedaccording to the standards BS EN ISO 1716 and ASTMD2015. The maximumamount of heat that the sample can release under highly idealizedconditions was determined in an oxygen bomb calorimeter using adiabaticand isothermal methods. This test determines the maximum total heatrelease of the material after complete combustion, i.e. the differencebetween the gross heat of combustion and the residual heat after 2 hoursof combustion. A gross heat of combustion of 85 KJ/Kg was determined,meaning that the product is considered as an extremely non combustiblematerials (M0).

Mechanical tests were also performed on the sample according to the NBNEN 196-1 standards. It was determined that the product had the followingproperties modulus of rupture 15.5 Mpa, compressive strength 30-40 Mpa,young's modulus 2200-4500 Mpa.

The water capillary porosity was of about 13-14% (ASTM C948-81).

1. A composition comprising at least: an inorganic binder having calciumsilicate sites which are connected the one with the other byalumina-silica phosphate bonds, the calcium silicate sites acting ascross-linking sites for the alumina-silica phosphate bonds with a weightratio Al₂O₃/SiO₂ ranging from 0.3:1 and 10:1, and silicon containingfibers with a length of less than 1000 μm, the weight content of siliconcontaining fibers with a length of less than 1000 μm in the compositionafter its hardening and after removal of the possible free water beingof at least 0.5%.
 2. The composition of claim 1, which comprises siliconcontaining fibers with an average (in weight) length of less than 500μm, the weight content of silicon containing fibers with an averagelength of less than 500 μm in the composition after its hardening andafter removal of the possible free water being of at least 0.5%.
 3. Thecomposition of claim 1, which comprises silicon containing fibers withan average (in weight) length of more than 10 μm.
 4. The composition ofclaim 1, which comprises silicon containing fibers with an average (inweight) length of more than 20 μm.
 5. The composition of claim 1, whichcomprises silicon containing fibers with an average (in weight) lengthcomprised between 25 μm and 300 μm.
 6. The composition of claim 1, whichcomprises silicon containing fibers with an average (in weight) lengthbetween 50 μm and 250 μm.
 7. The composition of claim 1, in which thesilicon containing fibers with a length of less than 1000 μm aresubstantially not reactive with the binder.
 8. The composition of claim1, in which the silicon containing fibers with a length of less than 500μm are substantially not reactive with the binder.
 9. The composition ofclaim 1, in which the silicon containing fibers with a length of lessthan 1000 μm are not reactive with the binder.
 10. The composition ofclaim 1, in which the silicon containing fibers with a length of lessthan 500 μm are not reactive with the binder.
 11. The composition ofclaim 1, which, after hardening and removal of free water, comprisesfrom 1% up to 85% by weight, silicon containing fibers with a length ofless than 1000 μm, which are substantially not reactive with the binder.12. The composition of claim 1, which, after hardening and removal offree water, comprises from 1% up to 85% by weight, silicon containingfibers with a length of less than 1000 μm, which are not reactive withthe binder.
 13. The composition of claim 1, which, after hardening andremoval of free water, comprises from 2% up to 75% by weight, siliconcontaining fibers with a length of less than 1000 μm, which are notreactive with the binder.
 14. The composition of claim 1, which, afterhardening and removal of free water, comprises from 1% up to 85% byweight, silicon containing fibers with a length of less than 500 μm,which are not reactive with the binder.
 15. The composition of claim 1,which, after hardening and removal of free water, comprises from 2% upto 75% by weight, silicon containing fibers with a length of less than500 μm, which are not reactive with the binder.
 16. The composition ofclaim 1, which, after hardening and removal of free water, comprisesfrom 20% up to 65% by weight silicon containing fibers with a length ofless than 1000 μm which are substantially not reactive with the binder.17. The composition of claim 1, which, after hardening and removal offree water, comprises from 30% up to 60% by weight silicon containingfibers with a length of less than 500 μm, which are not reactive withthe binder.
 18. The composition of claim 1, which further comprisessilica flour with a particle size of less than 500 μm, the weightcontent of silica flour in the composition after its hardening and afterremoval of the possible free water being of at least 0.5%.
 19. Thecomposition of claim 1, which further comprises silica flour with anaverage (in weight) particle size comprised between 2 and 100 μm, theweight content of silica flour in the composition after its hardeningand after removal of the possible free water being comprised between 1and 10%.
 20. The composition of claim 1, which further comprises silicaflour with an average (in weight) particle size comprised between 2 and100 μm, the weight content of silica flour in the composition after itshardening and after removal of the possible free water being comprisedbetween 2 and 8%.
 21. The composition of claim 1, which furthercomprises silica flour with an average (in weight) particle sizecomprised between 5 and 60 μm, the weight content of silica flour in thecomposition after its hardening and after removal of the possible freewater being comprised between 2 and 8%.
 22. The composition of claim 1,which further comprises silica flour with an average (in weight)particle size comprised between 10 and 50 μm the weight content ofsilica flour in the composition after its hardening and after removal ofthe possible free water being comprised between 2 and 8%.
 23. Thecomposition of claim 1, which further comprises crystallized aluminasilicate particles which are substantially not reactive with the binderand which have an average (in weight) particle size comprised between 5and 100 μm, the weight content of non reactive crystallized aluminasilicate in the composition after its hardening and after removal of thepossible free water being comprised between 1 and 10%.
 24. Thecomposition of claim 1, which further comprises crystallized aluminasilicate particles which are substantially not reactive with the binderand which have an average (in weight) particle size comprised between 5and 100 μm, the weight content of non reactive crystallized aluminasilicate in the composition after its hardening and after removal of thepossible free water being comprised between 2 and 8%.
 25. Thecomposition of claim 1, in which the calcium silicate sites of theinorganic binder act as cross-linking sites for the alumina-silicaphosphate bonds with a weight ratio Al₂O₃/SiO₂ ranging from 0.6:1 and6:1.
 26. The composition of claim 1, in which the weight ratio calciumsilicate site/SiO₂ present in the alumina-silica phosphate bonds of theinorganic binder is greater than
 1. 27. The composition of claim 1, inwhich the weight ratio calcium silicate site/SiO₂ present in thealumina-silica phosphate bonds of the inorganic binder is greater than1.5.
 28. The composition of claim 1, in which the calcium silicate sitesof the inorganic binder are calcium meta silicate sites having asubstantially acicular nature with a length/diameter ratio from 2/1 to50/1.
 29. The composition of claim 1, in which the calcium silicatesites of the inorganic binder are calcium meta silicate sites having asubstantially acicular nature with a length/diameter ratio from 3/1 to20/1.
 30. The composition of claim 28, in which the calcium metasilicate sites has an average length from 10 μm to 10 mm.
 31. Thecomposition of claim 29, in which the calcium meta silicate sites has anaverage length from 50 μm to 5 mm.
 32. The composition of claim 1, inwhich the weight ratio calcium silicate sites/alumina-silica phosphatebonds of the inorganic binder is comprised between 0.1 and 1.1.
 33. Thecomposition of claim 1, in which the weight ratio calcium silicatesites/alumina-silica phosphate bonds of the inorganic binder iscomprised between 0.3 and 0.9.
 34. The composition of claim 1, in whichthe weight ratio calcium silicate sites/alumina-silica phosphate bondsof the inorganic binder is comprised between 0.4 and 0.7.
 35. A processfor the preparation of a composition according to claim 1 comprising atleast an inorganic binder having calcium silicate sites which areconnected the one with the other by alumina-silica phosphate bonds, thecalcium silicate sites acting as cross-linking sites for thealumina-silica phosphate bonds with a weight ratio Al₂O₃/SiO₂ rangingfrom 0.3:1 and 10:1, and silicon-containing fibers with a length of lessthan 1000 μm, the weight content of silicon containing fibers with alength of less than 1000 μm in the composition after its hardening andafter removal of the possible free water being of at least 0.5%, inwhich said inorganic binder is prepared by mixing insoluble calciumsilicate particles with an acid alumina-silica phosphate solution at atemperature lower than 50° C., said acid alumina-silica phosphatesolution comprising solubilized SiO₂ and having a pH of less than 2,said alumina-silica phosphate solution having a weight ratio Al₂O₃/SiO₂ranging from 0.3:1 and 10:1.
 36. The process of claim 35, in which waterinsoluble calcium silicate particles are mixed with an acidalumina-silica phosphate solution at a temperature lower than 50° C.said acid alumina-silica phosphate solution comprising solubilized SiO₂and having a pH of less than 1.5, said alumina-silica phosphate solutionhaving a weight ratio Al₂O₃/SiO₂ ranging from 0.6:1 and 6:1.
 37. Theprocess of claim 35, in which water insoluble calcium silicate particlesare mixed with an acid alumina-silica phosphate solution at atemperature lower than 50° C., said acid alumina-silica phosphatesolution comprising solubilized SiO₂ and having a pH comprised between0.5 and 1.5, said alumina-silica phosphate solution having a weightratio Al₂O₃/SiO₂ ranging from 0.6:1 and 6:1.
 38. The process of claim35, in which the weight ratio water insoluble calcium silicateparticles/solubilized SiO₂ present in the alumina-silica phosphatesolution is greater than
 1. 39. The process of claim 35, in which theweight ratio water insoluble calcium silicate particles/solubilized SiO₂present in the alumina-silica phosphate solution is greater than 1.5.40. The process of claim 35, in which the calcium silicate particles arecalcium meta silicate particles having a substantially acicular naturewith a length/diameter ratio from 2/1 to 50/1.
 41. The process of claim35, in which the calcium silicate particles are calcium meta silicateparticles having a substantially acicular nature with a length/diameterratio from 3/1 to 20/1.
 42. The process of claim 40, in which thecalcium meta silicate particles have an average length from 10 μm to 10mm.
 43. The process of claim 42, in which the calcium meta silicateparticles have an average length from 50 μm to 5 mm.
 44. The process ofclaim 35, in which the calcium silicate particles act as cross-linkingsites for alumina-silica phosphate bonds.
 45. The process of claim 35,in which the weight ratio calcium silicate particles/alumina-silicaphosphate solution is comprised between 0.1 and 1.1.
 46. The process ofclaim 35, in which a filler is mixed with the calcium silicate particlesbefore being mixed with the acid alumina-silica phosphate solution. 47.The process of claim 35, in which a filler is mixed to the mixturecalcium silicate/alumina-silica phosphate solution, before itshardening.
 48. The process of claim 35, in which the hardening of thebinder is carried out at a temperature comprised between 0° C. and 50°C.
 49. The process of claim 35, in which the binder is hardened underpressure.
 50. The process of claim 35, in which the amount of calciumsilicate added to the acid silica alumina phosphate solution is suchthat the weight ratio calcium silicate/SiO₂ present in the acid solutionis comprised between 1 and
 5. 51. The process of claim 35, in which theamount of calcium silicate added to the acid silica alumina phosphatesolution is such that the weight ratio calcium silicate/SiO₂ present inthe acid solution is comprised between 1.5 and 3.5.
 52. The process ofclaim 35, in which the amount of calcium silicate added to the acidsilica alumina phosphate solution is such that the weight ratio calciumsilicate/SiO₂ present in the acid solution is greater than
 2. 53. Theprocess of claim 35, in which the acid silica alumina phosphate solutionis prepared by mixing a silica-alumina mixture with an acid consistingsubstantially only of phosphoric acid.
 54. The process of claim 53, inwhich further silica and alumina is added to the formed acid solution.55. The process of claim 35, in which the acid silica alumina phosphatesolution is prepared by mixing silica particles with an acid consistingsubstantially only of phosphoric acid, and by mixing thereafter to thesilica containing solution alumina particles.
 56. The process of claim35, in which the acid silica alumina phosphate solution is prepared bymixing alumina particles with an acid consisting substantially only ofphosphoric acid, and by mixing thereafter to the alumina containingsolution silica particles.
 57. The process of claim 35, in which theacid silica alumina phosphate solution is prepared at least by mixingprecipitated silica with an acid solution with a pH lower than 1.5. 58.The process of claim 35, in which inert silicon containing fibers with alength of less than 1000 μm are mixed to the mixture calciumsilicate/alumina-silica phosphate solution, before its completehardening.
 59. The process of claim 35, in which inert siliconcontaining fibers with a length of less than 1000 μm are mixed to thealumina-silica phosphate solution before the adding of water insolublecalcium silicate particles.
 60. The process of claim 35, in which inertsilicon containing fibers with a length of less than 1000 μm and waterinsoluble calcium silicate particles are added together to thealumina-silica phosphate solution.
 61. A process for the manufacture ofa product comprising a support provided with at least a hardened layercomprising an inorganic binder having calcium silicate sites which areconnected the one with the other by alumina-silica phosphate bonds, thecalcium silicate sites acting as cross-linking sites for thealumina-silica phosphate bonds with a weight ratio Al₂O₃/SiO₂ rangingfrom 0.3:1 and 10:1, in which at least partly a face of the support iscontacted with a composition comprising at least: an inorganic binderhaving calcium silicate sites which are connected the one with the otherby alumina-silica phosphate bonds, the calcium silicate sites acting ascross-linking sites for the alumina-silica phosphate bonds with a weightratio Al₂O₃/SiO₂ ranging from 0.3:1 and 10:1, silicon containing fiberswith a length of less than 1000 μm, the weight content of siliconcontaining fibers with a length of less than 1000 μm in the compositionafter its hardening and after removal of the possible free water beingof at least 0.5%, and a further filler, and in which the composition ishardened on said support.
 62. The process of claim 61, in which thecomposition contacting the support comprises silicon containing fiberswith a length of less than 100 μm, the weight content of siliconcontaining fibers with a length of less than 1000 μm in the compositionafter its hardening and after removal of the possible free water beingof at least 0.5%.
 63. The process of claim 61, in which at least aportion of a face of the support not contacted with the composition isprovided with a water repellent coating.
 64. The process of claim 63, inwhich the water repellent coating is a fluoro silicon coating.
 65. Theprocess of claim 61, in which at least one face of the support intendedto be not contacted with the composition is provided with a waterrepellent coating.
 66. The process of claim 65, in which at least partlya face of the support is provided with a water repellent coating priorcontacting at least partly a face of the support with the composition.67. The process of claim 61, in which at least a portion of a faceadjacent to a portion of a face provided with a hardened layer areprovided with a water repellent coating.
 68. The composition of claim 1,which further comprises silica flour with a particle size of lesscomprised between 2 and 400 μm, the weight content of silica flour inthe composition after its hardening and after removal of the possiblefree water being of at least 0.5%.
 69. A product comprising at least ahardened layer prepared by hardening a composition comprising at least:an inorganic binder having calcium silicate sites which are connectedthe one with the other by alumina-silica phosphate bonds, the calciumsilicate sites acting as cross-linking sites for the alumina-silicaphosphate bonds with a weight ratio Al₂O₃/SiO₂ ranging from 0.3:1 and10:1; silicon-containing fibers with a length of less than 1000 μm, theweight content of silicon containing fibers with a length of less than1000 μm in the composition after its hardening and after removal of thepossible free water being of at least 0.5%; and a further filler, saidhardened layer comprising: an inorganic binder having calcium silicatesites which are connected the one with the other by alumina-silicaphosphate bonds, the calcium silicate sites acting as cross-linkingsites for the alumina-silica phosphate bonds with a weight ratioAl₂O₃/SiO₂ ranging from 0.3:1 and 10:1; silicon-containing fibers with alength of less than 1000 μm; and a further filler.
 70. The product ofclaim 69, in which the hardened layer covers at least partly a face of asupport element.
 71. The product of claim 69, in which the hardenedlayer covers at least partly a face of a support comprising a core whichcan be subjected to a water swelling, and in which at least partly aface not covered by hardened layer is provided with a water repellentcoating.
 72. The product of claim 71, in which the water repellentcoating is a silicon containing water repellent coating.
 73. The productof claim 72, in which the water repellent coating is a fluoro siliconcoating.
 74. The product of claim 69, in which the hardened layer coversat least partly a face of a support comprising a core which can besubjected to a water swelling, and in which the faces not with ahardened layer are provided with a water repellent coating.
 75. Theproduct of claim 74, in which the water repellent coating is a siliconcontaining water repellent coating.
 76. The product of claim 69, inwhich the hardened layer covers at least partly a face of a supportcomprising a core which can be subjected to a water swelling, said facebeing provided with a water repellent coating.
 77. The product of claim69, in which the hardened layer comprises at least: an inorganic binderhaving calcium silicate sites which are connected the one with the otherby alumina-silica phosphate bonds, the calcium silicate sites acting ascross-linking sites for the alumina-silica phosphate bonds with a weightratio Al₂O₃/SiO₂ ranging from 0.3:1 and 10:1, and silicon containingfibers with a length of less than 1000 μm, the weight content of siliconcontaining fibers with a length of less than 1000 μm in the compositionafter its hardening and after removal of the possible free water beingof at least 0.5%.
 78. The product of claim 77, which comprises siliconcontaining fibers with an average (in weight) length of less than 500μm, the weight content of silicon containing fibers with an averagelength of less than 500 μm in the composition after its hardening andafter removal of the possible free water being of at least 0.5%.
 79. Theproduct of claim 69, in which the hardened layer comprises siliconcontaining fibers with an average (in weight) length of more than 10 μm.80. The product of claim 69, in which the hardened layer comprisessilicon containing fibers with an average (in weight) length of morethan 20 μm.
 81. The product of claim 69, in which the hardened layercomprises silicon containing fibers with an average (in weight) lengthcomprised between 25 μm and 300 μm.
 82. The product of claim 69, inwhich the hardened layer comprises silicon containing fibers with anaverage (in weight) length between 50 μm and 250 μm.
 83. The product ofclaim 69, in which the hardened layer comprises silicon containingfibers with a length of less than 1000 μm which are substantially notreactive with the binder.
 84. The product of claim 69, in which thehardened layer comprises silicon containing fibers with a length of lessthan 500 μm which are substantially not reactive with the binder. 85.The product of claim 69, in which the hardened layer comprises siliconcontaining fibers with a length of less than 1000 μm, which are notreactive with the binder.
 86. The product of claim 69, in which thehardened layer comprises silicon containing fibers with a length of lessthan 500 μm which are not reactive with the binder.
 87. The product ofclaim 69, in which, after hardening and removal of free water, thehardened layer comprises from 1% up to 85% by weight, silicon containingfibers with a length of less than 1000 μm, which are substantially notreactive with the binder.
 88. The product of claim 69, in which, afterhardening and removal of free water, the hardened layer comprises from1% up to 85% by weight, silicon containing fibers with a length of lessthan 1000 μm, which are not reactive with the binder.
 89. The product ofclaim 69, in which, after hardening and removal of free water, thehardened layer comprises from 2% up to 75% by weight, silicon containingfibers with a length of less than 1000 μm, which are not reactive withthe binder.
 90. The product of claim 69, in which, after hardening andremoval of free water, the hardened layer comprises from 1% up to 85% byweight, silicon containing fibers with a length of less than 500 μm,which are not reactive with the binder.
 91. The product of claim 69, inwhich, after hardening and removal of free water, the hardened layercomprises from 2% up to 75% by weight, silicon containing fibers with alength of less than 500 μm, which are not reactive with the binder. 92.The product of claim 69, in which, after hardening and removal of freewater, the hardened layer comprises from 20% up to 65% by weight siliconcontaining fibers with a length of less than 1000 μm which aresubstantially not reactive with the binder.
 93. The product of claim 69,in which, after hardening and removal of free water, the hardened layercomprises from 30% up to 60% by weight silicon containing fibers with alength of less than 500 μm, which are not reactive with the binder. 94.The product of claim 69, in which the hardened layer further comprisessilica flour with a particle size of less than 500 μm, the weightcontent of silica flour in the composition after its hardening and afterremoval of the possible free water being of at least 0.5%.
 95. Theproduct of claim 69, in which the hardened layer further comprisessilica flour with a particle size of less comprised between 2 and 400μm, the weight content of silica flour in the composition after itshardening and after removal of the possible free water being of at least0.5%.
 96. The product of claim 69, in which the hardened layer furthercomprises silica flour with an average (in weight) particle sizecomprised between 2 and 100 μm the weight content of silica flour in thecomposition after its hardening and after removal of the possible freewater being comprised between 1 and 10%.
 97. The product of claim 69, inwhich the hardened layer further comprises silica flour with an average(in weight) particle size comprised between 2 and 100 μm, the weightcontent of silica flour in the composition after its hardening and afterremoval of the possible free water being comprised between 2 and 8%. 98.The product of claim 69, in which the hardened layer further comprisessilica flour with an average (in weight) particle size comprised between5 and 60 μm, the weight content of silica flour in the composition afterits hardening and after removal of the possible free water beingcomprised between 2 and 8%.
 99. The product of claim 69, in which thehardened layer further comprises silica flour with an average (inweight) particle size comprised between 10 and 50 μm the weight contentof silica flour in the composition after its hardening and after removalof the possible free water being comprised between 2 and 8%.
 100. Theproduct of claim 69,in which the hardened layer further comprisescrystallized alumina silicate particles which are substantially notreactive with the binder and which have an average (in weight) particlesize comprised between 5 and 100 μm, the weight content of non reactivecrystallized alumina silicate in the composition after its hardening andafter removal of the possible free water being comprised between 1 and10%.
 101. The product of claim 69, in which the hardened layer furthercomprises crystallized alumina silicate particles which aresubstantially not reactive with the binder and which have an average (inweight) particle size comprised between 5 and 100 μm, the weight contentof non reactive crystallized alumina silicate in the composition afterits hardening and after removal of the possible free water beingcomprised between 2 and 8%.
 102. The product of claim 69, in which thecalcium silicate sites of the inorganic binder act as cross-linkingsites for the alumina-silica phosphate bonds with a weight ratioAl₂O₃/SiO₂ ranging from 0.6:1 and 6:1.
 103. The product of claim 69, inwhich the weight ratio calcium silicate site/SiO₂ present in thealumina-silica phosphate bonds of the inorganic binder is greaterthan
 1. 104. The product of claim 69, in which the weight ratio calciumsilicate site/SiO₂ present in the alumina-silica phosphate bonds of theinorganic binder is greater than 1.5.
 105. The product of claim 69, inwhich the calcium silicate sites of the inorganic binder are calciummeta silicate sites having a substantially acicular nature with alength/diameter ratio from 2/1 to 50/1.
 106. The product of claim 69, inwhich the calcium silicate sites of the inorganic binder are calciummeta silicate sites having a substantially acicular nature with alength/diameter ratio from 3/1 to 20/1.
 107. The product of claim 105,in which the calcium meta silicate sites has an average length from 10μm to 10 mm.
 108. The product of claim 106, in which the calcium metasilicate sites has an average length from 50 μm to 5 mm.
 109. Theproduct of claim 69, in which the weight ratio calcium silicatesites/alumina-silica phosphate bonds of the inorganic binder iscomprised between 0.1 and 1.1.
 110. The product of claim 69, in whichthe weight ratio calcium silicate sites/alumina-silica phosphate bondsof the inorganic binder is comprised between 0.3 and 0.9.
 111. Theproduct of claim 69, in which the weight ratio calcium silicatesites/alumina-silica phosphate bonds of the inorganic binder iscomprised between 0.4 and 0.7.